CN103855381A - Modified preparation method of high-temperature power type lithium manganate LiMn2-x-yMIxMIIyO4-zF2z - Google Patents

Modified preparation method of high-temperature power type lithium manganate LiMn2-x-yMIxMIIyO4-zF2z Download PDF

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CN103855381A
CN103855381A CN201410069856.4A CN201410069856A CN103855381A CN 103855381 A CN103855381 A CN 103855381A CN 201410069856 A CN201410069856 A CN 201410069856A CN 103855381 A CN103855381 A CN 103855381A
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compound
manganese
limn
lithium salts
high temperature
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陈国华
陈申
覃旭松
邓远富
施志聪
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Guangzhou HKUST Fok Ying Tung Research Institute
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Guangzhou HKUST Fok Ying Tung Research Institute
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    • C—CHEMISTRY; METALLURGY
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1207—Permanganates ([MnO]4-) or manganates ([MnO4]2-)
    • C01G45/1214—Permanganates ([MnO]4-) or manganates ([MnO4]2-) containing alkali metals
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H01M4/1315—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H01M4/13915—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a modified preparation method of a high-temperature power type lithium manganate LiMn2-x-yMIxMIIyO4-zF2z. The preparation method is as follows: a porous micron spherical manganese source and an eutectic molten lithium system are adopted as raw materials, metal ions and F-ions are doped and calcination is performed to prepare a lithium manganate positive electrode material. The prepared positive electrode material formed by calcining has the characteristics of regular appearance, big tap density, high power and long service life. The novel preparation method also successfully controls the appearance of a product and the defect of a crystal structure and improves the magnification performance and high temperature cycling performance of the lithium manganate anode material; besides, the preparation method adopts a simple preparation technique, and is moderate in synthesis temperature and applicable to large-scale production.

Description

A kind of high temperature power-type LiMn2O4 LiMn 2-x-ym ixm iIyo 4-zf 2zmodification method for preparing
Technical field
The present invention relates to lithium ion battery electrode material preparation, be specifically related to a kind of high temperature power-type LiMn2O4 LiMn 2-x-ym i xm iI yo 4-zf 2zmodification method for preparing.
Background technology
Manganese (Mn) element reserves in earth's surface are abundant, and with low cost, especially the manganese resource of China occupies first of countries in the world, therefore develops LiMn2O4 (LiMn 2o 4) anodal utmost point material, can greatly reduce the cost of lithium ion battery.As anode material for lithium-ion batteries, it has excellent multiplying power and overcharging resisting performance, is the good positive electrode that one is applicable to the electrical source of power of electric tool and electric motor car (comprising LEV (Light Electric Vehicle) and electric automobile).But the LiMn of spinel structure 2o 4capacity (55 ℃) under cyclic process and hot conditions decay too fastly, be its further major obstacle of the marketization of restriction.For many years, high-end LiMn2O4 product is mainly manufactured by Japan and South Korean venture, and is applied to electric automobile field.The domestic research and development at high-end LiMn2O4 are in a backward condition relatively, seldom make a breakthrough.Most researchers is thought, causes spinelle LiMn 2o 4the poor principal element of cycle performance is: the dissolving of Mn in electrolyte, decomposition and the Jahn-Teller effect of electrolyte.In order to improve LiMn 2o 4capacity attenuation situation, researcher has carried out doping vario-property to material, to improve its cycle performance and structural stability.For example, adopt rare earth element, cation (as Li +, Co 3+, Ni 2+deng) adulterate and improve spinelle LiMn 2o 4structural stability, reduce the destruction of charge and discharge process to material structure.
The composition of manganate cathode material for lithium, pattern with and corresponding preparation method the performance of material is had to very large impact, therefore, on the patent of invention (201210139968.3) that the present invention had previously applied in this team and the basis of (201210311508.4), a kind of power-type extended-life lithium ion battery positive electrode LiMn is disclosed 2-x-ym i x m iI yo 4-zf 2z(M i=Li, M iI=Al, Cr, Mn, one or more of the metals such as Fe and Co) and the novel preparation method of such material.Namely LiMn2O4 being carried out in the process of metal cation doping, appropriate F synchronously adulterates ?ion.About F ?ion doping is to LiMn 2o 4the impact of chemical property mainly there are two kinds of viewpoints: the first viewpoint is thought F ?doping can make part Mn 4+be reduced to Mn 3+thereby, improved the specific capacity of material; In addition, due to F ?the strong sucking action of ion, makes material structure more stable, has effectively alleviated LiMn in cyclic process 2o 4capacity attenuation; The second viewpoint is thought F ?ion doping, in improving specific capacity, can make the lattice of material distort, thereby produce obvious Jahn-Teller effect.So to F ?the control of ions dosage becomes key of the present invention.
The present invention utilizes eutectic lithium salts system, manganese salt, metal cation compound (Al, Cr, Mn, the metal ion compound such as Fe and Co) synchronize codope with anionic compound (fluoride) according to certain ratio, through mechanical mixture, under certain temperature and condition, porous microsphere shape LiMn is prepared in calcining 2-x-ym i x m iI yo 4-zf 2z(M i=Li, M iI=Al, Cr, Mn, one or more of the metals such as Fe and Co) positive electrode.LiMn prepared by the method 2-x-ym i x m iI yo 4-zf 2zmaterial pattern is regular, tap density is large, specific capacity is high, high rate performance and high temperature cyclic performance excellence, is desirable power-type anode material for lithium-ion batteries.Electrochemical results shows, LiMn prepared by the method 2-x-ym i x m iI yo 4-zf 2z(M i=Li, M iI=Al, Cr, Mn, one or more of the metals such as Fe and Co) positive electrode is at 25 ℃, and under 1 and 10 C multiplying powers, its initial specific capacity is respectively 115 and 100 mAh/g; Under 1 C multiplying power, circulate after 1500 circles, its capability retention is 83.9%; Under 10 C multiplying powers, circulate after 2500 circles, its capability retention is 91%.At 55 ℃, the initial specific capacity under 5 C multiplying powers is 114 mAh/g; After circulation 1000 circles, its capability retention is 80%.Preparation technology of the present invention is simple, easy to operate, and synthesis temperature is moderate, without specific (special) requirements, pollution-free to environment, is suitable for scale enlarged reproduction.
Summary of the invention
The object of this invention is to provide the novel preparation method of a kind of Stability Analysis of Structures, high temperature power-type anode material for lithium-ion batteries that security performance is good, i.e. a kind of high temperature power-type LiMn2O4 LiMn 2-x-ym i xm iI yo 4-zf 2zmodification method for preparing.
Realizing the method that above-mentioned purpose adopts is to utilize the spherical mangano-manganic oxide of multi-pore micron/manganese dioxide/carbon acid manganese presoma as template, and in conjunction with the novel synthetic of Eutectic molten salt technology and cation, the synchronous codope of anion.Preparation technology's key step of the present invention is as follows:
Take the compound of manganese, eutectic lithium salts as raw material, the compound of synchronous doping metals compound and F is prepared the anode material for lithium-ion batteries LiMn of high performance micron-size spherical structure after batch mixing and calcining 2-x-ym i x m iI yo 4-zf 2z, wherein M i=Li, M iI=Al, Cr, Mn, one or more in Fe or Co, its concrete grammar is:
(1) by the compound of the compound of reactant manganese, eutectic lithium salts, metallic compound and F, mechanical mixture is even; If exist containing F lithium salts in eutectic lithium salts, do not need to add the compound of F, wherein in reactant, the mixing molar ratio of each material is Mn:Li:M iI: F=(2- x- y): (1+ x): y:2z, wherein: x=0～0.10, y=0～0.10, z=0～0.075; The compound of described manganese comprises the oxide of manganese or the carbonate of manganese; Described metallic compound is more than one in oxide, hydroxide, carbonate or the nitrate of metal, and wherein metal is M iIbe Al, Cr, Mn, Fe or Co;
(2) 90～120 ℃ of insulations 1～3 hour, be raised to 300～500 ℃ with the heating rate of 5～10 ℃/min, keep 1～3 hour; Be raised to 600～900 ℃ with the heating rate of 5～10 ℃/min again, keep 6～12 hours; Then products therefrom is naturally cooled to room temperature, after taking-up, be gained end product LiMn2O4 LiMn 2-x-ym i x m iI yo 4-zf 2z, wherein M i=Li, M iI=Al, Cr, Mn, more than one in Fe or Co metal.
In said method, the oxide of described manganese is MnO 2or Mn 3o 4in more than one; The carbonate of described manganese is MnCO 3.
In said method, described eutectic lithium salts is LiOHH 2o, LiCl, LiNO 3, Li 2cO 3or two or more in LiF, its eutectic point temperature is 300～500 ℃.
In said method, the compound of described F comprises LiF, NH 4hF 2or AlF 3in more than one.
In said method, described LiMn2O4 LiMn 2-x-ym i xm iI yo 4-zf 2zfor positive electrode, there is the micron-size spherical structure that nano particle is reunited.
Gained positive electrode of the present invention has height ratio capacity, high power, life-span length and high temperature cyclic performance advantageous feature.
Advantage of the present invention and positive effect are:
(1) technique of the present invention is simple, easy to operate, and without specific (special) requirements, pollution-free to environment, synthesis temperature is moderate, and energy resource consumption is low, is suitable for scale enlarged reproduction.
(2) the present invention, by calcining after presoma and eutectic lithium salts and doped metal ion compound, anionic compound mechanical mixture, both can prepare micro-nano spherical LiMn 2-x-ym i x m iI yo 4-zf 2z(M i=Li, M iI=Al, Cr, Mn, one or more of the metals such as Fe and Co) positive electrode, can utilize again doping metals to change the crystal microscopic structure of lithium manganate material, thereby improve the chemical property of material.
(3) the present invention adopts eutectic synthesis preparation method, not only can avoid running into Yu Meng source, lithium source in the synthetic lithium manganate material of conventional high-temperature solid phase method and mix inhomogeneous problem, also make material structure further stable because of adulterated metal cation and anion, effectively alleviated the decay of material capacity in cyclic process.
(4) lithium manganate material that prepared by employing the present invention is as the positive electrode active materials of lithium rechargeable battery, there is higher charging and discharging capacity, excellent high temperature cyclic performance and high rate performance, be desirable high-energy-density power lithium-ion battery positive electrode, there is wide market application foreground.
Accompanying drawing explanation
Fig. 1 is the Li of embodiment 1 1.04mn 1.94co 0.04o 3.95f 0.1the SEM figure of product.
Fig. 2 is the Li of embodiment 1 1.04mn 1.94co 0.04o 3.95f 0.1the XRD figure of product.
Fig. 3 is the Li of embodiment 1 1.04mn 1.94co 0.04o 3.95f 0.1the first circle charging and discharging curve figure of product, wherein a curve is discharge curve, b curve is charging curve.
Fig. 4 is the Li of embodiment 1 1.04mn 1.94co 0.04o 3.95f 0.1the cycle performance performance map (1 C multiplying power) of product at 25 ℃.
Fig. 5 is the Li of embodiment 1 1.04mn 1.94co 0.04o 3.95f 0.1product is in 25 ℃ of cycle performance performance map (10 C multiplying power).
Fig. 6 is the Li of embodiment 1 1.04mn 1.94co 0.04o 3.95f 0.1(M i=Li, M iI=Co) the cycle performance figure (5 C multiplying power) of product at 55 ℃.
Fig. 7 is the LiMn of embodiment 1 2-x-ym i x m iI yo 4-zf 2z(M i=Li, M iI=Co) impact of doped F ion pair material property.
 
Embodiment
Be below specific embodiment, introduce in detail content of the present invention.It is for the ease of understanding this patent invention that embodiment is provided, and is never the invention of restriction this patent.
Multi-pore micron level spherical structure LiMn provided by the present invention 2-x-ym i x m iI yo 4-zf 2z(M i=Li, M iI=Al, Cr, Mn, one or more of the metals such as Fe and Co) material is applied to lithium rechargeable battery as positive electrode active materials.
The LiMn of following instance 1～4 preparation 2-x-ym i x m iI yo 4-zf 2z(M i=Li, M iI=Co, Al) product XRD, SEM and TEM(HTEM) characterize assembled battery, wherein positive electrode active materials LiMn simultaneously 2-x-ym i x m iI yo 4-zf 2z, conductive agent acetylene black and binding agent Kynoar (PVDF) stir according to the ratio of mass ratio 8:1:1 or ball milling mixes, and adds appropriate 1-METHYLPYRROLIDONE solvent to make slurry; Slurry is brushed on aluminium foil, after dry, compressing tablet as anodal; With the LiPF containing 1 mol/L 6eC/DEC/DMC(volume ratio be 1:1:1) for electrolyte, polypropylene porous film is barrier film, metal lithium sheet is negative pole, in argon gas glove box, is assembled into button cell.On instrument, carry out charge-discharge performance test discharging and recharging.
embodiment 1
Eutectic lithium salts system is by LiOHH 2o, Li 2cO 3with LiF composition, the ratio of these three kinds of lithium salts is 0.54:0.2:0.1; Eutectic lithium salts, porous microsphere shape Mn 3o 4presoma and Co 3o 4after the ratio that is 1.04:1.94:0.04 according to the mol ratio of Li:Mn:Co is fully mixed, 105 ℃ of insulations 2 hours, with the heating rate of 7 ℃/min, temperature is raised to after 360 ℃, be incubated 1.5 hours, then with the heating rate of 7 ℃/min by after temperature increase to 780 ℃, continue calcining 10 hours, obtain black product.The product obtaining is made respectively to SEM(referring to Fig. 1) with XRD(referring to Fig. 2) analyze, result shows that product is Li 1.04mn 1.94co 0.04o 3.95f 0.1.
The spherical Li preparing with above-mentioned condition 1.04mn 1.94co 0.04o 3.95f 0.1for electrolyte and the barrier film of positive electrode active materials and coupling, be assembled into CR2025 type battery.At room temperature (25 ℃), it is under 3.2～4.4 V conditions that charge/discharge is pressed, and with the multiplying power charge/discharge of 1 C, the first circle specific discharge capacity of this material is that 115 mAh/g(are referring to Fig. 3), after 1200 circle circulations, capability retention is that 83.9%(is referring to Fig. 4); With the multiplying power charge/discharge of 10 C, the specific capacity of this material is 102 mAh/g, and after circulation 2500 circles, capability retention is that 91%(is referring to Fig. 5).In addition by this material at high temperature (55 ℃), with 5 C multiplying power charge/discharge, circulation 1000 circle capability retentions be that 80%(is referring to Fig. 6).
, the more important thing is meanwhile, at high temperature (55 ℃), under 1 C multiplying power charge/discharge condition, lithium manganate material after doped F ion, performance be obviously better than the undoping material property (referring to Fig. 7) of F ion.
embodiment 2
Eutectic lithium salts system is by LiOHH 2o, Li 2cO 3with LiF composition, the ratio of these three kinds of lithium salts is 0.56:0.2:0.1; Eutectic lithium salts, porous microsphere shape Mn 3o 4presoma and and Al 2o 3after the ratio that is 1.06:1.92:0.04 according to Li:Mn:Al mol ratio is fully mixed, 105 ℃ of insulations 2 hours, with the heating rate of 7 ℃/min, temperature is raised to after 360 ℃, be incubated 1.5 hours, then with the heating rate of 7 ℃/min by after temperature increase to 780 ℃, continue calcining 10 hours, obtain black product.The product obtaining is made respectively to SEM and XRD analysis, and result shows that product is Li 1.06mn 1.92al 0.04o 3.95f 0.1.
With the spherical Li preparing under above-mentioned condition 1.06mn 1.92al 0.04o 3.95f 0.1for electrolyte and the barrier film of positive electrode active materials and coupling, be assembled into CR2025 type battery.At room temperature (25 ℃), it is under 3.2～4.4 V conditions that charge/discharge is pressed, and with the multiplying power charge/discharge of 1 C, the first circle specific discharge capacity of this material is 113 mAh/g, and after circulation 1200 circles, capability retention is 81.5%; With the multiplying power charge/discharge of 10 C, the specific capacity of this material is 98 mAh/g, and after circulation 2500 circles, capability retention is 81%.In addition by this material at high temperature (55 ℃), with 5 C multiplying power charge/discharge, circulation 1000 circle capability retentions be 80%.
embodiment 3
Eutectic lithium salts system is by LiOHH 2o, Li 2cO 3with LiF composition, the ratio of these three kinds of lithium salts is 0.56:0.2:0.1; Eutectic lithium salts, porous microsphere shape Mn 3o 4and Co 3o 4after the ratio that is 1.06:1.92:0.04 according to Li:Mn:Co mol ratio is fully mixed, 105 ℃ of insulations 2 hours, with the heating rate of 7 ℃/min, temperature is raised to after 360 ℃, be incubated 1.5 hours, then with the heating rate of 7 ℃/min by after temperature increase to 780 ℃, continue calcining 10 hours, obtain black product.The product obtaining is made respectively to SEM and XRD analysis, and result shows that product is Li 1.06mn 1.92co 0.04o 3.95f 0.1.
With the spherical Li preparing under above-mentioned condition 1.06mn 1.92co 0.04o 3.95f 0.1for electrolyte and the barrier film of positive electrode active materials and coupling, be assembled into CR2025 type battery.At room temperature (25 ℃), it is under 3.2～4.4 V conditions that charge/discharge is pressed, and with the multiplying power charge/discharge of 1 C, the first circle specific discharge capacity of this material is 114 mAh/g, and after circulation 1200 circles, capability retention is 82%; With the multiplying power charge/discharge of 10 C, the specific capacity of this material is 98 mAh/g, and after circulation 2500 circles, capability retention is 82.3%.In addition by this material at high temperature (55 ℃), with 5 C multiplying power charge/discharge, circulation 1000 circle capability retentions be 81%.
embodiment 4
Eutectic lithium salts system is by LiOHH 2o, Li 2cO 3with LiF composition, the ratio of these three kinds of lithium salts is 0.54:0.2:0.1; Eutectic lithium salts, porous microsphere shape Mn 3o 4and Co 3o 4after the ratio that is 1.07:1.97:0.01 according to Li:Mn:Co mol ratio is fully mixed, 105 ℃ of insulations 2 hours, with the heating rate of 7 ℃/min, temperature is raised to after 360 ℃, be incubated 1.5 hours, then with the heating rate of 7 ℃/min by after temperature increase to 780 ℃, continue calcining 10 hours, obtain black product.The product obtaining is made respectively to SEM and XRD analysis, and result shows that product is Li 1.07mn 1.97co 0.01o 3.95f 0.1.
With the spherical Li preparing under above-mentioned condition 1.07mn 1.97co 0.01o 3.95f 0.1for electrolyte and the barrier film of positive electrode active materials and coupling, be assembled into CR2025 type battery.At room temperature (25 ℃), it is under 3.2～4.4 V conditions that charge/discharge is pressed, and with the multiplying power charge/discharge of 1 C, the first circle specific discharge capacity of this material is 119 mAh/g, and after circulation 1200 circles, capability retention is 78%; With the multiplying power charge/discharge of 10 C, the specific capacity of this material is 103 mAh/g, and after circulation 2500 circles, capability retention is 75%.In addition by this material at high temperature (55 ℃), with 5 C multiplying power charge/discharge, circulation 1000 circle capability retentions be 70%.
Above-mentioned concrete execution mode is the doping way of optimum execution mode of the present invention, the especially kind of the composition of eutectic lithium salts system, doped metal ion, F ion and the selection of doping ratio and corresponding calcining heat.But above-mentioned embodiment can not limit claim of the present invention, other is any does not deviate within technical scheme of the present invention is included in protection scope of the present invention.

Claims (5)

1. a high temperature power-type LiMn2O4 LiMn 2-x-ym i xm iI yo 4-zf 2zmodification method for preparing, it is characterized in that, take the compound of manganese, eutectic lithium salts as raw material, the compound of synchronous doping metals compound and F is prepared the anode material for lithium-ion batteries LiMn of high performance micron-size spherical structure after batch mixing and calcining 2-x-ym i x m iI yo 4-zf 2z, wherein M i=Li, M iI=Al, Cr, Mn, one or more in Fe or Co, its concrete grammar is:
(1) by the compound of the compound of reactant manganese, eutectic lithium salts, metallic compound and F, mechanical mixture is even; If exist containing F lithium salts in eutectic lithium salts, do not need to add the compound of F, wherein in reactant, the mixing molar ratio of each material is Mn:Li:M iI: F=(2- x- y): (1+ x): y:2z, wherein: x=0～0.10, y=0～0.10, z=0～0.075; The compound of described manganese comprises the oxide of manganese or the carbonate of manganese; Described metallic compound is more than one in oxide, hydroxide, carbonate or the nitrate of metal, and wherein metal is M iIbe Al, Cr, Mn, Fe or Co;
(2) 90～120 ℃ of insulations 1～3 hour, be raised to 300～500 ℃ with the heating rate of 5～10 ℃/min, keep 1～3 hour; Be raised to 600～900 ℃ with the heating rate of 5～10 ℃/min again, keep 6～12 hours; Then products therefrom is naturally cooled to room temperature, after taking-up, be gained end product LiMn2O4 LiMn 2-x-ym i x m iI yo 4-zf 2z, wherein M i=Li, M iI=Al, Cr, Mn, more than one in Fe or Co metal.
2. a kind of high temperature power-type LiMn2O4 LiMn according to claim 1 2-x-ym i xm iI yo 4-zf 2zmodification method for preparing, it is characterized in that, the oxide of described manganese is MnO 2or Mn 3o 4in more than one; The carbonate of described manganese is MnCO 3.
3. a kind of high temperature power-type LiMn2O4 LiMn according to claim 1 2-x-ym i xm iI yo 4-zf 2zmodification method for preparing, it is characterized in that, described eutectic lithium salts is LiOHH 2o, LiCl, LiNO 3, Li 2cO 3or two or more in LiF, its eutectic point temperature is 300～500 ℃.
4. a kind of high temperature power-type LiMn2O4 LiMn according to claim 1 2-x-ym i xm iI yo 4-zf 2zmodification method for preparing, it is characterized in that, the compound of described F comprises LiF, NH 4hF 2or AlF 3in more than one.
5. a kind of high temperature power-type LiMn2O4 LiMn according to claim 1 2-x-ym i xm iI yo 4-zf 2zmodification method for preparing, it is characterized in that described LiMn2O4 LiMn 2-x-ym i xm iI yo 4-zf 2zfor positive electrode, there is the micron-size spherical structure that nano particle is reunited.
CN201410069856.4A 2014-02-28 2014-02-28 Modified preparation method of high-temperature power type lithium manganate LiMn2-x-yMIxMIIyO4-zF2z Pending CN103855381A (en)

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CN109360981A (en) * 2018-09-05 2019-02-19 中北大学 Cell positive material LiCrxMn2-xO4-yFyAnd the preparation method of positive plate
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Application publication date: 20140611